A degradation mechanism of polystyrene (PS) in mealworms reared on expanded PS (EPS) was investigated by its decrease in molecular weight and change in chemical structure. A 33% decrease in molecular weight was observed for the digested PS in the frass after 1 week of feeding to mealworms. The FT-IR and py-GC/MS spectra of the digested PS showed radical oxidative reactions taking place in the mealworm body. The presence of hydroperoxide, alcohol and phenol groups was confirmed, and dimer fragments of styrene with quinone and phenol groups were obtained. The decrease in molecular weight and the alternation of benzene rings indicated that autoxidation and quinonization via phenolic intermediates occurred simultaneously in the mealworm body. The survival rate of mealworms reared on EPS was higher than that of starved worms, indicating that EPS was a nutrient source. However, no weight gain was observed in mealworms fed EPS alone. Comparison with the mixed diets with bran or urethane foams (PU) indicated that protein, phosphorus and magnesium components absent from EPS were required for mealworm growth.